Azo compounds containing two 6-hydroxypyrid-2-one coupling component radicals the nitrogen atoms of which are linked by a biscationic radical

Abstract

Compounds of the formula <IMAGE> wherein each A is independently linear or branched C2-6alkylene or linear or branched C3-6alkylene substituted by hydroxy, each D is independently the radical of a diazo component of the benzene, azobenzene or naphthalene series, E is a divalent radical attached to each -N(+)R3R4- radical through an aliphatic carbon atom, each R1 is independently hydrogen, C1-4alkyl, cyclohexyl, phenyl or phenyl(C1-2alkyl), each R2 is independently hydrogen, cyano, -COOR5, -CONR6R7 or <IMAGE> wherein R5 is hydrogen, C1-4alkyl or phenyl(C1-2alkyl), each of R6 and R7 is independently hydrogen or C1-4alkyl, each R8 is independently C1-4alkyl, and r is 0, 1, 2 or 3, each R3 is independently C1-4alkyl or C1-4alkyl monosubstituted by halo, cyano, hydroxy or phenyl, each R4 is independently hydrogen, C1-4alkyl or C1-4alkyl monosubstituted by halo, cyano, hydroxy or phenyl, each An(-) is a non-chromophoric anion, and n is 0, 1, 2, 3, 4, 5 or 6, with the proviso that the negative charges of the An(-)'s balance the positive charge of each cationic group of the molecule not balanced by the negative charge of an anionic group of the molecule, compositions containing them and their use for dyeing and printing hydroxy group- or nitrogen-containing organic substances.

What is claimed is: 
     
       1. A compound of the formula ##STR58## or a mixture thereof, wherein each A is independently linear or branched C 2-6  alkylene or linear or branched C 3-6  alkylene substituted by hydroxy, each D is independently the radical of a diazo component of the benzene, azobenzene or naphthalene series,   E 1a  is linear or branched C 2-4  alkylene; linear or branched C 3-4  alkylene monosubstituted by hydroxy; linear or branched C 2-6  alkylene interrupted by --O--, --NR 9  -- or ##STR59##  or linear or branched C 3-8  alkylene monosubstituted or disubstituted by hydroxy and interrupted by --O--, --NR 9  -- or ##STR60##  wherein R 9  is hydrogen or C 1-6  alkyl, and R 10  is hydrogen, halo, C 1-4  alkyl or C 1-4  alkoxy,     each R 1  is independently hydrogen, C 1-4  alkyl, cyclohexyl, phenyl or phenyl(C 1-2  alkyl),   each R 2  is independently hydrogen, cyano, --COOR 5 , --CONR 6  R 7  or ##STR61##  wherein R 5  is hydrogen, C 1-4  alkyl or phenyl(C 1-2  alkyl), each of R 6  and R 7  is independently hydrogen or C 1-4  alkyl,   each R 8  is independently C 1-4  alkyl, and r is 0, 1, 2 or 3,     each R 3  is independently C 1-4  alkyl or C 1-4  alkyl monosubstituted by halo, cyano, hydroxy or phenyl,   each R 4  is independently hydrogen, C 1-4  alkyl or C 1-4  alkyl monosubstituted by halo, cyano, hydroxy or phenyl   each An⊖ is a non-chromophoric anion, and   n is , 1, 2, 3, 4, 5 or 6, with the proviso that the negative charges of the An⊖'s balance the positive charge of each cationic group of the molecule not balanced by the negative charge of an anionic group of the molecule.     
     
     
       2. A compound according to claim 1. 
     
     
       3. A compound according to claim 2 wherein each D is independently the radical of a diazo component of the benzene, azobenzene or naphthalene series containing a substitutent selected from sulfo, carboxy and sulfamoyl. 
     
     
       4. A compound according to claim 2 wherein each halo is fluoro, chloro or bromo, with the provisos that (i) the number of cationic groups exceeds the number of anionic groups, and (ii) each hydroxy substituent of each alkyl group and alkylene radical bonded to a nitrogen atom is bonded to a carbon atom that is not directly bonded to a nitrogen atom. 
     
     
       5. A compound according to claim 2 wherein each R 1  is independently methyl, ethyl, cyclohexyl, phenyl or benzyl. 
     
     
       6. A compound according to claim 2 wherein each R 2  is independently hydrogen, cyano, --COOR 5a , ##STR62## wherein each of R 5a , R 6a  and R 7a  is independently hydrogen, methyl or ethyl. 
     
     
       7. A compound according to claim 2 wherein each R 3  is independently methyl, ethyl or 2-hydroxyethyl, and   each R 4  is independently hydrogen, methyl, ethyl or 2-hydroxyethyl.   
     
     
       8. A compound according to claim 2 wherein each A is independently is linear or branched C 2-4  alkylene or linear or branched C 3-4  alkylene monosubstituted by hydroxy.   
     
     
       9. A compound according to claim 2 wherein each D is independently ##STR63## wherein R 11  is hydrogen, halo, nitro, C 1-4  alkyl, C 1-4  alkoxy, carboxy, --Q 1  --(NR 12  --Q 2 ) q  --NR 13  R 14 , --Q 1  --(NR 12  --Q 2 ) q  --NR⊕ 15  R 16  R 17 , ##STR64## R 18  is hydrogen or sulfo, and R 19  is hydrogen, sulfo, carboxy or sulfamoyl, wherien   Q 1  is a direct bond, --CO--, --NR 12a  --NHCOCH 2  -- or --SO 2  --, wherein R 12a  is hydrogen or methyl, and the * denotes the atom that is bonded to a carbon atom of the ring to which R 11  is bonded,   Q 2  is linear or branched C 2-8  alkylene; linear or branched C 3-6  alkylene substituted by hydroxy; linear or branched C 1-6  alkylene-1,3-phenylene; linear or branched C 1-6  alkylene-1,4-phenylene; 1,3-phenylene or 1,4-phenylene,   each R 10  is independently hydrogen, halo, C 1-4  alkyl or C 1-4  alkoxy,   R 12  is hydrogen or C 1-4  alkyl,     each of R 13  and R 14  is independently hydrogen; C 1-6  alkyl; C 2-6  alkyl monosubstituted by hydroxy or cyano; phenyl; phenyl substituted by one to three substituents selected from chloro, C 1-4  alkyl and C 1-4  alkoxy; phenyl(C 1-4  alkyl); phenyl(C 1-4  alkyl) the phenyl ring of which is substituted by one to three substituents selected from chloro, C 1-4  alkyl and C 1-4  alkoxy; Chd 5-6cycloalkyl; or C 5-6  cycloalkyl substituted by one to three C 1-4  alkyl group; or   --NR 13  R 14  is piperidino; piperazino; morpholino; or piperidino, piperazino or morpholino substituted by one or two C 1-4  alkyl gruops,   each of R 15  and R 16  is independently C 1=6  alkyl; C 2-6  alkyl monosubstituted by hydroxy or cyano; phenyl; phenyl substituted by one to three substituents selected from chloro, C 1-4  alkyl and C 1-4  alkoxy; phenyl(C 1-4  alkyl); phenyl(C 1-4  alkyl) the phenyl ring of which is substituted by one to three substituents selected from chloro, C 1-4  alkyl and C 1-4  alkoxy; C 5-6  cycloalkyl; or C 5-6  cycloalkyl substituted by one to three C 1-4  alkyl groups, R 17  is C 1-4  alkyl or benzyl, or ⊖   --NR 15  R 16  R 17  is pyridinium; methylpyridinium; dimethylpyridinium; N-R 17  -piperidinium; N-R 17  -piperazinium; N-R 17  -morpholinum; or N-R 17  -piperidinium, N-R 17  -piperazinium or N-R 17  -morpholinium substituted by one or two C 1-4  alkyl groups, wherein R 17  is C 1-4  alkyl or benzyl, and   q is 0 or 1.   
     
     
       10. A compound according to claim 9 having the formula ##STR65## wherien each A 2  is independently linear or branched C 2-4  alkylene, each D b  is independently ##STR66##  wherein R 11a  is hydrogen, chloro, nitro, methyl, methoxy, carboxy, ##STR67##  wherien Q 1a  is a direct bond, --CO--, --NR 12a  --NHCOCH 2  -- or --SO 2  --,  wherein the * denotes the atom that is bonded to a carbon atom of the ring to which R 11a  is bonded,     Q 2a  is linear or branched C 2-3  alkylene,   each of R 13a  and R 14a  is independently hydrogen, methyl or ethyl, or   --NR 13a  R 14a  is piperidino, piperazino or morpholino,   each of R 15a  and R 16a  is independently methyl or ethyl, and   R 17a  is methyl, ethyl or benzyl, or   --NR⊕ 15a  R 16a  R 17a  is pyridinium, methylpyridinium, N-R 17a  -piperidinium, N-R 17a  -piperazinium or N-R 17a  -morpholinium, wherein   R 17a  is methyl, ethyl or benzyl, and q is 0 or 1,     R 18  is hydrogen or sulfo, and   R 19  is hydrogen, sulfo, carboxy or sulfamoyl,     E 2a  is linear or branched C 2-  alkylene; linear or branched C 3-4  alkylene monosubstituted by hydroxy; or --Qa--X--Qa--, wherein each Qa is independently linear or branched C 1-3  alkylene or linear or branched C 3-4  alkylene monosubstituted by hydroxy, and   X is --NR 9a  -- or ##STR68##  wherein R 9a  is hydrogen or C 1-4  alkyl,     each R 1a  is independently methyl, ethyl, cyclohexyl, phenyl or benzyl,   each R 2a  is independently hydrogen, cyano, --COOR 5a , --CONR 6a  R 7a  or ##STR69##  wherein each of R 5a , R 6a  and R 7a  is independently hydrogen, methyl or ethyl, and r is 0, 1, 2 or 3,     each R 3b  is independently methyl, ethyl or 2-hydroxyethyl,   each R 4b  is independently hydrogen, methyl, ethyl or 2-hydroxyethyl, and n is 0, 1, 2, 3, 4, 5 or 6,   wherein each R 10a  is independently hydrogen, chloro, methyl or methoxy,   R 12a  is hydrogen or methyl, and   each An⊖ is a non-chromophoric anion, with the provisos that (i) the negative charges of the An⊖'s balance the positive charge of each catnionic group of the molecule not balanced by the negative charge of an anionic group of the molecule, and (ii) when a D b  contains one anionic group, the total number of the cationic groups present in the molecule exceeds the number of the anionic groups in both D b  groups.     
     
     
       11. A compound according to claim 10 with the proviso that any hydroxy substituent of an alkylene radical bonded to a nitrogen atom is bonded to a carbon atom that is not directly bonded to a nitrogen atom. 
     
     
       12. A compound according to claim 10 wherein each A 2  is independently --(CH 2 ) p'  --,   each D b  is independently ##STR70##  wherein R 11b  is hydrogen, chloro, nitro, methyl, methoxy, phenyl, phenylamino, sulfamoyl, --CO--NR 12a  --Q 2a  --NR 13a  R 14a  or --CO--NR 12a  --Q 2a  --NR 15a  R 16a  R 17a , E 2a  is linear or branched C 2-3  alkylene, C 3-4  alkylene monosubstituted by hydroxy or --CH 2  --phenylene--CH 2  --,     each R 1a  is independently methyl or ethyl,   each R 2a  is independently hydrogen, --COOR 5a , --CONHR 7a , pyridinium or methylpyridinium, and   each R 3b  and R 4b  is methyl.   
     
     
       13. A compound according to claim 12 wherein the A 2  's are identical, the D b  's are identical,     the R 1a  's are identical, and   the R 2a  's are identical.   
     
     
       14. A compound according to claim 12 wherein each R 1a  is methyl,   each R 2a  is independently pyridinium or methylpyridinium,   each R 18  is hydrogen, and   each R 19  is hydrogen.   
     
     
       15. A compound according to claim 14 wherein the A 2  's are identical,   the D b  's are identical, and   the R 2a  's are identical.   
     
     
       16. A compound according to claim 15 with the proviso that any hydroxy substitutent of an alkylene radical bonded to a nitrogen atom is bonded to a carbon atom that is not directly bonded to a nitrogen atom. 
     
     
       17. A compound according to claim 16 having the formula ##STR71## wherein each An⊖ is a non-chromophoric anion. 
     
     
       18. A compound according to claim 17 wherien each An⊖ is chloride or acetate. 
     
     
       19. A storage-stable, aqueous liquid dye composition containing a compound according to claim 1 in water-soluble salt form.